GIRRAJ GOVT. COLLEGE,(AUTONOMOUS) NIZAMABAD DEPARTMENT OF CHEMISTRY III YEAR SYLLABUS V SEMESTER Unit – I (Inorganic Chemistry) (1 h/w) 1. Coordination Chemistry: IUPAC nomenclature, bonding theories – review of Werner’s theory and Sidgwick’s concept of coordination, Valence bond theory, geometries of coordination numbers 4-tetrahedral and square planar and 6-octahedral and its limitations, crystal filed theory, splitting of d-orbitals in octahedral, tetrahedral and square-planar complexes – low spin and high spin complexes – factors affecting crystalfield splitting energy, merits and demerits of crystalfield theory. Isomerism in coordination compounds – structural isomerism and stereo isomerism, stereochemistry of complexes with 4 and 6 coordination numbers. 2. Spectral and magnetic properties of metal complexes: Electronic absorption spectrum of [Ti(H2O)6]3+ ion. Types of magnetic behavior, spin-only formula, calculation of magnetic moments, experimental determination of magnetic susceptibility – Gouy method UNIT – II (Organic Chemistry ) (1h/w) 1. Nitrogen compounds 9 h Nitro hydrocarbons: Nomenclature and classification – nitro hydrocarbons – structure. Tautomerism of nitroalkanes leading to aci and keto form. Preparation of Nitroalkanes. Reactivity – halogenation, reaction with HONO (Nitrous acid), Nef reaction and Mannich reaction leading to Michael addition and reduction. Amines (Aliphatic and Aromatic): Nomenclature, Classification into 10, 20, 30 Amines and Quarternary ammonium compounds. Preparative methods -1. Ammonolysis of alkylhalides 2. Gabriel synthesis 3. Hoffman’s bromamide reaction (mechanism). 4. Reduction of Amides and Schmidt reaction. Physical properties and basic character – Comparative basic strength of Ammonia, methyl amine, dimethyl amine, trimethyl amine and aniline – comparative basic strength of aniline, Nmethylaniline and N,N-dimethyl aniline (in aqueous and non-aqueous medium), steric effects and substituent effects. Use of amine salts as phase transfer catalysts. Chemical properties: a) Alkylation b) Acylation c) Carbylamine reaction d) Hinsberg separation e) Reaction with Nitrous acid of 10, 20, 30 (Aliphatic and aromatic amines). Electrophilic substitutions of Aromatic amines – Bromination and Nitration. oxidation of aryl and 30 Amines. Diazotization Cyanides and isocyanides: Nomenclature (aliphatic and aromatic) structure. Preparation of cyanides from a) Alkyl halides b) from amides c) from aldoximes. Preparation of isocyanides from Alkyl halides and Amines. Properties of cyanides and isocyanides, a) hydrolysis b) addition of Grignard reagent iii) reduction iv) oxidation. 2. Amino acids and proteins 5 h Introduction: Definition of Amino acids, classification of Amino acids into alpha, beta, and gama amino acids. Natural and essential amino acids – definition and examples, classification of alpha amino acids into acidic, basic and neutral amino acids with examples. Methods of synthesis: General methods of synthesis of alpha amino acids (specific examples – Glycine, Alanine, valine and leucene) by following methods: a) from halogenated carboxylic acid b) Malonic ester synthesis c) strecker’s synthesis. Physical properties: Optical activity of naturally occurring amino acids: L-configuration, irrespective of sign rotation, Zwitterion structure – salt like character - solubility, melting points, amphoteric character , definition of isoelectric point. Chemical properties: General reactions due to amino and carboxyl groups – lactams from gamma and delta amino acids by heating peptide bond (amide linkage). Structure and nomenclature of peptides and proteins. Unit-III (physical chemistry) (1 h / w) 1. Chemical kinetics 9 h Rate of reaction, factors influencing the rate of a reaction-concentration, temperature, pressure, solvent, light, catalyst. Experimental methods to determine the rate of reaction. Definition of order and molecularity. Derivation of rate constants for first, second, third and zero order reactions and examples. Derivation for time half change. Methods to determine the order of reactions. Kinetics of complex reactions (first order only): opposing reactions, parallel reactions, consecutive reactions and chain reactions. Effect of temperature on rate of reaction, Arrhenius equation, concept of activation energy. Theories of reaction rates- collision theory-derivation of rate constant for bimolecular reaction. The transition state theory (elementary treatment). Unit-IV (General chemistry) (1 h / w) 1. Heterocyclic Compounds 5 h Introduction and definition: Simple 5 membered ring compounds with one hetero atom Ex. Furan. Thiophene and pyrrole. Importance of ring system – presence in important natural products like hemoglobin and chlorophyll. Numbering the ring systems as per Greek letter and Numbers. Aromatic character – 6- electron system (four-electrons from two double bonds and a pair of non-bonded electrons from the hetero atom). Tendency to undergo substitution reactions. Resonance structures: Indicating electron surplus carbons and electron deficient hetero atom. Explanation of feebly acidic character of pyrrole, electrophillic substitution at 2 or 5 position, Halogenation, Nitration and Sulphonation under mild conditions. Reactivity of furan as 1,3diene, Diels Alder reactions (one example). Sulphonation of thiophene purification of Benzene obtained from coal tar). Preparation of furan, Pyrrole and thiophene from 1,4,- dicarbonyl compounds only, Paul-Knorr synthesis, structure of pyridine, Basicity – Aromaticity – Comparison with pyrrole – one method of preparation and properties – Reactivity towards Nucleophilic substitution reaction – chichibabin reaction. 2. Photochemistry 5 h Difference between thermal and photochemical processes. Laws of photochemistry- GrothusDraper’s law and Stark-Einstein’s law of photochemical equivalence. Quantum yield. Ferrioxalate actinometry. Photochemical hydrogen- chlorine, hydrogen-bromine reaction. Jablonski diagram depicting various processes occurring in the excited state, qualitative description of fluorescence, phosphorescence, non-radiative processes (internal conversion, intersystem crossing). Photosensitized reactions- energy transfer processes (simple example). LABORATORY COURSE – III Practical Paper – III (Organic Chemistry) 90 hrs (3 h / w) 1. Synthesis of Organic Compounds i. Aromatic electrophilic substitution Nitration: Preparation of nitro benzene and p-nitro acetanilide, Halogenation: Preparation of p-bromo acetanilide – preparation of 2,4,6-tribromo phenol. ii. Diazotization and coupling: Preparation of pheyl azo β-napthol iii. Oxidation: Preparation of benzoic acid from benzoyl chloride iv. Reduction: Preparation of m-nitro aniline from m-dinitro benzene v. Esterfication: Preparation of methyl p-nitro benzoate from p-nitro benzoic acid. vi. Methylation: Preparation of β-napthyl methyl ether Condensation: Preparation of benzilidine aniline and Benzoyl aniline. 2. Thin layer Chromatography & Column Chromatography i. Preparation of the TLC plates. Checking the purity of the compounds by TLC: Acetylation of salicyclic acid, aniline, Benzoylation of Aniline and Phenol Determination of Rf values and identification of organic compounds by TLC: preparation and separation of 2,4dinitrophenyl hydrazones of acetione and 2-butanone using toluene and light petroleum(40:60) ii. Separation of ortho & para nitro aniline mixture by column chromatography 3. Organic Qualitative Analysis: i. Identification of an organic compound through the functional group analysis, determination of melting point and preparation of suitable derivatives. ii. Separation of two component mixtures 1) Aniline + Naphthalene 2) Benzoic acid + Benzophenone 3) p-Cresol + Chlorobenzene. 4. Demonstration experiments: 1. Steam distillation experiment: separation of ortho and para nitro phenols 2) Microwave assisted Green synthesis, two examples: 1. Hydrolysis of Benzamide 2. Oxidation of Toluene LABORATORY COURSE – IV Practical Paper IV (Physical Chemistry) 90hrs (3 h / w) 1. Chemical kinetics i. Determination of specific reaction rate of the hydrolysis of methyl acetate catalyzed by hydrogen ion at room temperature. ii. Determination of rate of decomposition of hydrogen peroxide. iii. Determination of overall order of saponification of ethyl acetate 2. Distribution law i. Determination of distribution coefficient of iodine between water and carbon Tetrachloride. ii. Determination of molecular status and partition coefficient of benzoic acid in Toluene and water. 3. Electrochemistry i. Determination of concentration of HCl conductometrically using standard NaOH solution. ii. Determination of concentration of acetic acid conductometrically using standard NaOH solution. iii. Determination of dissociation constant (Ka) of acetic acid by conductivity measurements. iv. Determination of solubility and solubility product of BaSO4. v. Determination of redox potentials of Fe2+/Fe3+by potentiometric titration of ferrous ammonium sulphate vs. potassium dichromate. 4. pH metry i. Preparation phosphate buffer solutions ii. pH metric titration of weak acid, acetic acid with strong base NaOH and calculation of dissociation constant. 5. Colorimetry i. Verification of Beer-Lambert law for KMnO4 , K2Cr2O7 and determination of concentration of the given solution. ii. Verification of Beer-Lambert law for CuSO4 and determination of concentration of the given solution. iii. Composition of complex of Cu2+ - EDTA disodium salt 6. Adsorption i. Surface tension and viscosity of liquids. ii. Adsorption of acetic acid on animal charcoal, verification of Freundlich isotherm. 7. Project Work: Collection of spectral data of a minimum of six compounds belonging to different functional groups (other than those included in the syllabus) and submission of the report. NOTE: Apart from the experiments (1 to 6) the project work (7) shall also be included in the University Examination.